Lubricant compositions



2,948,680 LUBRICANT COMPOSITIONS Ellis K. Fields, Chicago, "111.,assignor to Standard Oil Company, Chicago, 111., a corporation ofIndiana No Drawing. Filed Mar. '15, 1957,*Ser. No. 646,219

10 Claims. "(CL 252-323) This invention relates to improvements inlubricants "faces, especially bearings of the hard metal alloy type.

Many oils are not well suited-as lubricants for use in internalcombustion engines, particularly those of the type operating undersevere conditions, since under such severe operating conditions the oilsare susceptible to "oxidative' deterioration, resulting 'in thedevelopment of carbonaceous and/ or resinous orsimilarvarnish-likedeposits intheen'gine and on and about-the'valvesand rings'of'the'engine. Furthermore, such lubricants oftendevelopproducts ofoxidative deteriorationwhich are corrosive,"par ticularly to thebearings of the hard metal alloy type, such as copper-lead bearings,cadmiumsilver bear- "ings, etc., Which'are'frequ'ently used in suchengines.

"It is an object of the present invention to provide additives for oils,particularly hydrocarbon oils such as-mineral "oils,'which willstabilize such oils against oxidativedeterioration and which will rendersuch oilsnon-corr-osive.

'It is another' object of the invention to provide lubricants "forinternal combustion engines which do not'form carbonaceous deposits orresinous varnish-like materials on and about'the valves, pistons andrings of-such engines and which are not corrosive to metals,particularly to hard 'a'lloy'bearings metals of the copper-lead andcadmium- 'silve'r type.

In'accor'dance with the present invention, the foregoi'n'g objects canbeattained by incorporating in'an Oleaginous'material, such as for examplea lubricating oil, a

small, but corrosion and/ or oxidation inhibiting, amount of anoil-soluble compound selected'f-rom the class'of. a compound having thegeneral structuralformula in which R and R" areradicals-selected'fromthe'cla'ss consisting of hydrogen, a'hydrocarbon radical, and'aheterocyclic radical containing from 1 to about 40 carbon atoms, R is ahydrocarbon radical of from 1 to about'40 carbon atoms, and X representsthe remainder ofthe nucleus of an N-hetero ring selected'from thegroupconsisting of S-and 6-membered N-hetero rings inwhi'chfl if; 1C

hydrogen is attaced to the hetero nitrogen atom. The

hydrocarbon radical can be acyclic, alicyclic, or an aryl monoorpoly-nuclear radical. When R and/or R" is a heterocyclic radical, it maycontain an S-, N-, or O-heteroatom. The hydrocarbon and heterocyclicradicals can rcontain substituentl-groups such as alkyl, aryl, "alk'oxy,aryloxy, halogen, hydroxy, amino, cyano, etc. groups.

The oil-soluble compounds of the type I above described can be obtained'by reacting 8-quinolinol with an azomethine having the general formulaR'-:OH='N--R in which R and R are as above described in molar proportionof 1:1 at a temperature of from about 50 C. to

about C. for. 0.5 to about 18 hours.

"The -az'omethines'"a'remeadily -prepared by 'well known:*means-by'reactingin mole ratio of. 1 :1 analiphatic,cycloaliphatic,aromaticcr' heterocyclic amine'of from T1 to about lO carbon-atoms withan aliphatic, cycloaliphatic', aromatic" or heterocyclic aldehyde offrom 1 to about 18 carbon atoms.

The oil-soluble "compounds 'of'the type II above de- -sc"ribed '--are"obtainable by reacting 8-'quinolinol with :a nitrogen heterocycliccompound,having ahy'drogen atom attached to the N-hetero' atom and analdehyde as above described. Examples of suitable N-heterocycliccompoundsare piperidine, tetrahydropyrrole, py-tetrahydroquinoline;andpy-tetrahydroisoquinoline.

Preferably, the oil-soluble compounds of types Itan'd "IPaboveareprepared'by reacting amixture of the amine 'or" theN=heterocycliccompound, the aldehydeand the S-quinolinol in moleproportions of 151:1 at a temperature of from about 5-0- C.to about 110C. for a period of. time fromabout 0.5 .to.about l8.:hours. rlf desired,the reactions can 1 be carried out in the presence. of a sol- "ve'ntsuch as dioxane, benzene or the like. 7 7

Specific compounds illustrative. of the above defined class are thefollowing:

in bJ-o-td lI1 CnHis HzaCrz-N wherein Z in each of the above formulasstands for the S-quinolinol radical (III) Although the above-described8-quinolinol-azometbine reaction products all exhibit, to a definitedegree, anticorrosion and anti-oxidation properties, all are notnecessarily equivalent in their eifectiveness, since, depending areused, some variation in effectiveness may be exhibited. The preparationof 8-quinolinol-azomethine reaction products of the type hereinabovedescribed is illustrated by the following examples:

EXAMPLE I A mixture of 28.2 g. (0.2 mole) t-octyl azomethine (fromt-octyl primary amine and formaldehyde) and 29 g. (0.2 mole)8-quinolinol was heated at 220 F. for 1 hour. The product, 57 g., was aviscous, light orangebrown liquid. Analysis.-Calculated for C H N O:

N, 9.82. Found: N, 9.69.

EXAMPLE II A mixture of 29 g. (0.2 mole) 8-quinolinol, 17 g. (0.2 mole)t-butyl azomethine (made from t-butylamine and formaldehyde), and 50 cc.benzene was refluxed 30 minutes, then evaporated on the steam bath,giving 45 g. light brown, viscous product. Analysis.--Calculated for C HN O: C, 73.02; H, 7.82; N, 12.17. Found: C, 73.50; H, 7.51; N, 11.78.

EXAMPLE III A solution of 29 g. (0.2 mole) 8-quinolinol and 20.5 ml.(0.2 mole) diethylamine in 75 ml. ethyl alcohol was treated with 16.24ml. 37.3% aqueous formaldehyde (0.2 mole). Heat was evolved. Thesolution was kept at 131 F. for 1 hour, then stripped in vacuo, giving46 g. light brown, viscous product. Analysis.-Calculated for C H N O: N.11.42. Found: N, 11.13.

EXAMPLE V To a solution of 70.6 g. (0.2 mole) Armeen 2C (principally(n-C H NH) in 100 ml. isopropanol was added at 40 C. 16.24 ml. (0.2mole) 37.3% aqueous formaldehyde. The solution was stirred 5 minutes at40 C., 29 g. (0.2 mole) 8-quinolinol added, the mixture stirred 0.5 hourat 40 C., refluxed 1 hour, and blown with N at 90 C. till all volatilematerial was gone. The product, 100 g., was a light brown semi-solidmass. Analysis.- Calculated for C H N O: C, 80.00; H, 11.37; N, 5.49;mol. wt., 510. Found: C, 79.60; H, 10.75; N, 5.26; mol. Wt. 520.

. upon the nature and severity of the service in which they I EXAMPLEv11 A solution of 14.51 g. (0.1 mole) 8-quinolinol and 12.18 g. (0.1mole) 2-phenethylamine in 20 ml. dioxane was treated with 10.13 ml.benzaldehyde. The resulting solution was refluxed 1 hour, then blownwith N at 224 F. to strip all volatile material. The light-brown viscousproduct weighed 34.2 g. Analysis.--Calculated for C H N O; N. 7.91%.Found: N, 7.67%.

EXAMPLE VIII A solution of 14.51 g. (0.1 mole) 8-quinolinol, 9.9 ml.(0.1 mole) n-butylamine and 9.2 ml. (0.1 mole) OL-thiO- phenecarboxaldehyde in 20 m1. dioxane was refluxed 1 hour, then blown with Nat 224 F. till all volatile material was ofi. The dark brown viscousproduct weighed 28.4 g. Analysis.-Calculated for C H N OS; N, 8.98%; S,10.25%. Found: N, 8.88%; S, 9.89%.

The above-described reaction products can be used in amounts of fromabout 0.01% to about 10% and preferably from about 0.25% to about 5% incombination with lubricant base oils, such as hydrocarbon oils,synthetic hydrocarbon oils, such as those obtained'by the polymerizationof hydrocarbons, such as olefin polymers; synthetic lubricating oils ofthe alkylene-oxide type, for example, the Ucon oils," marketed byCarbide and Carbon Corporation, as well as other synthetic oils, such asthe polycarboxylic acid ester type oils, such as the esters of adipicacid, sebacic acid, maleic acid, azelaic acid, etc.

While the abovedescribed reaction products can be suitably employedalone in a base oil, they are usually used in combination with otherlubricant addition agents which impart various desired characteristicsto the base oil. Usually, these reaction products are used inconjunction with detergent-type additives, particularly those whichcontain sulfur or phosphorus and sulfur addition agents. This type isusually used in amounts of from about 0.002% to about 10%, andpreferably from about 0.01% to about 5%. Among the phosphorusandsulfurcontaining addition agents are the neutralized reaction productsof a phosphorus sulfide and a hydrocarbon, an alcohol, a ketone, anamine or an ester. Of the phosphorus sulfide reaction product additives,I prefer to employ the neutralized reaction products of a phosphorussulfide, such as a phosphorus pentasulfide, and a hydrocarbon of thetype described in U.S. 2,316,082, issued to C. M. Loane et al. April 6,1943. As taught in this patent, the preferred hydrocarbon constituent ofthe reaction is a mono-olefin hydrocarbon polymer resulting from thepolymerization of low molecular weight monoolefin hydrocarbons, such aspropylene, butenes, amylenes or copolymers thereof. Such polymers may beobtained by the polymerization of mono-olefins of less than six carbonatoms in the presence of a catalyst, such as sulfuric acid, phosphoricacid, boron fluoride, aluminum chloride, or other similar halidecatalysts of the Friedel- Crafts type.

The polymers employed are preferably mono-olefin polymers or mixtures ofmono-olefin polymers and isomono-olefin polymers having molecularweights ranging from about to 50,000 or more, and preferably from about500 to about 10,000. Such polymers can be obtained, for example, by thepolymerization in the liquid phase of a hydrocarbon mixture containingmonoand isomono-olefins, such as butylene and isobutylene at atemperature of from about ,80 F. to about 100 F. in the presence of ametal halide catalyst of the Friedel- Crafts type, such as for example,boron fluoride, aluminum chloride, and the like. In the preparation ofthese polymers, a hydrocarbon mixture containing isobutylene, butylenesand butancs recovered from petroleum gases, especially those gasesproduced in the cracking of petroleum oils in the manufacture ofgasoline, can be used.

Another suitable polymer is that obtained by polymerizing, in the liquidphase, a hydrocarbon mixture comprising substantially C hydrocarbons inthe presence of an aluminum chloride-complex catalyst. The catalyst ispreferably prepared by heating aluminum chloride with sesame. Thehydrocarbon mixture is introduced into the bottom of the reactor andpassed upward through the catalyst layer, while a temperature of fromabout 50 F. to about 110 F. is maintained in the reactor. The propaneand other saturated gases pass through the catalyst, while the propyleneis polymerized under these conditions. The propylene polymer can befractionated to any desired molecular weight, preferably from about 500to about 1,000 or higher. i 1

Essentially paraffinic hydrocarbons, such as bright stock residuums,lubricating oil distillate, petrolatums or paraffin waxes, may be used.There can also be employed the condensation products of any of theforegoing hydrocarbons, usually through first halogenating thehydrocarbons .and reacting with aromatic hydrocarbons in the presence ofanhydrous inorganic halides, such as aluminum chloride, zinc chloride,boron fluoride, and the like.

Examples of other high molecular weight olefinic hydrocarbons which canbe employed are cetene (C cerotene (C melene (C and mixed high molecularweight alkenes obtained by cracking petroleum oils.

Other preferred olefins suitable for the preparation of the phosphorussulfide reaction products are olefins having at least 20 carbon atoms inthe molecule of which from about 13 carbon atoms to about 18 carbonatoms, and preferably at least 15 carbon atoms, are in ,a long chain.Such volefins can be obtained by the dehydrogenation of alkyl halides,preferably long chain alkyl halides, particularly halogenated paraffinwaxes.

As a starting material there can be used the polymer or syntheticlubricating oil obtained by polymerizing unsaturated hydrocarbonsresulting from the vapor phase cracking of paraffin waxes in thepresence of aluminum chloride which is fully described in U.S. Patents1,955,260; 1,970,402 and 2,091,398. Still another type of olefin polymerwhich may be employed is the polymer resulting from the treatment ofvapor phase cracked gasoline and/ or gasoline fractions with sulfuricacid or solid adsorbents, such as fullers earth, whereby unsaturatedpolymerized hydrocarbons are removed. The reaction products of thephosphorus sulfide and the polymers resulting from the voltolization ofhydrocarbons as described, for example, in U.S. Patents 2,197,768 and2,191,787 are also suitable.

Other hydrocarbons that can be reacted with a phosphorus sulfide arearomatic hydrocarbons, such as for example, benzene, naphthalene,toluene, xylene, diphenyl, and the like, or an alkylated aromatichydrocarbon, such as for example, benzene having an alkyl substituenthaving at least four carbon atoms, and preferably at least eight carbonatoms, such as a long chain paraffin wax.

The phosphorus sulfide-hydrocarbon reaction product can be readilyobtained by reacting a phosphorus sulfide, for example, P 8 with thehydrocarbon at a temperature of from about 200 F. to about 500 F., andpreferably from about 200 F. to about 400 F., using from about 1% toabout 50%, and preferably from about 5% to about 25% of the phosphorussulfide in the reaction. It is advantageous to maintain a non-oxidizingatmosphere, such as, for example, an atmosphere of nitrogen above thereaction mixture. Usually, it is preferable to use an amount of thephosphorus sulfide that will completely react with the hydrocarbon sothat no further purification becomes necessary; however, an excessamount of'phos phorus sulfide can be used and separated from the productby filtration or by dilution with a hydrocarbon solvent, such as hexane,filtering and .subseqeuntly removing the slovent by suitable means, suchas by distillation. :If de sired the reaction product can be further{treated with steam at an elevated temperature of from about 100 F; toabout 600 F. 1 i

The phosphorus sulfide-hydrocarbon reaction product; when neutralizedwith a basic reagent containing a metal constituent, is characterized bythe presence or retention of the metal constituent of the basic reagent.v

The neutralized phosphorus sulfide hydrocarbon reaction product can beobtained by treatingthe acidic reaction product with a suitable basiccompound,such as hydroxide,

carbonate, oxide or sulfide of an alkaline earth metal or an alkalimetal, such as for example, potassium hydroxide, sodium hydroxide,sodium sulfide, calcium oxide, lime, barium hydroxide, barium oxide,etc. Other basic reagents can be used, such as, for example, ammonia oran alkyl or aryl-substituted ammonia, such as amines. The neutralizationof the phosphorus sulfide-hydrocarbon reaction product is carried outpreferably in a non-oxidizing atmosphere by contacting the acidicreaction product either as such or dissolved in a suitable solvent, suchas naphtha, with a solution of the basic reagent. As an alternativemethod, the reaction product can be treated with solid alkalinecompounds, such as KOH, NaOH, Na CO K 60 CaO, BaO, Ba(OH) Na s, and thelike, at an elevated temperature of from about F. to about 600 F.Neutralized reaction products containing a heavy metal constituent, suchas for example, tin, titanium, aluminum, chromium; cobalt, zinc, iron,and the like, can be obtained by reacting a salt of the desiredheavy'metal with the phosphorus sulfide-hydrocarbon reaction productwhich has been treated with a basic reagent, such as above'described.

Other phosphorus sulfide reaction products which can be used are thereaction products of a phosphorus sulfide and a fatty acid ester of thetype described in U.S. 2,399,243; the phosphorus sulfide-degras reactionproducts of U.S. 2,413,332; the reaction product of an alkylated phenolwith the condensation product of P 8 and turpentine of U.S. 2,409,877and U.S. 2,409,878; the reaction product of a phosphorus sulfide andstearonitrile of U.S. 2,416,807, etc.

The effectiveness of the herein-described S-quinoleneazomethine reactionproducts in inhibiting corrosion toward copper and/or leadeontainingmetals, such as for example, copper-lead alloys, and their oxidationinhibiting properties, are demonstrated by the data inTable I, obtainedby subjecting the above samples to the following test:

A copper-lead test specimen is lightly abraded with steel wool, Washedwith naphtha, dried and weighed to the near:

est milligram. The cleaned copper-lead test specimen is suspendedin asteel beaker, cleaned with a hot tnisodium phosphate solution, rinsedwith water, and acetone, and dried, and 250 grams of the oil to betested together with 0.625 gram lead oxide and 50 grams of a 30-35- meshsand charged to the beaker. The beaker is then placed in a bath orheating block and heated to a temperature of 300 F. (:2" F.) while thecontents are stirred by means of a stirrer rotating at 750 r.p.m. Thecontents of the beaker are maintained at this temperature fortwenty-four hours, after which the copper-lead test specimen is removed,rinsed with naphtha, dried and weighed. The test specimen is thenreplaced in the beaker and an additional 0.375 gram of lead oxide addedto the test oil. At the end of an additional twenty-four hours of testoperation the test specimen is again removed,

rinsed, and dried as before, and weighed. The test specimen is againplaced in the beaker together with an addi tional 0.250 gram of leadoxide and the test continued for another twenty-four hours (seventy-twohours total). At the conclusion of this time the test specimen isremoved I from the beaker, rinsed in naphtha, dried and weighed,

In addition to determining the weight loss of the metal specimen, theacidity of the oil is determined at the 24, 48, and 72 hour intervals.The loss in weight of the test specimen is recorded after each weighing.This test, known as the Sand Stirring Corrosion Test, is referred tohereinafter as S.S.C.T.

The following samples were subjected to the above test:

Sample A (control)--A solvent extracted SAE-30 base oil containing 4.3%of a barium-containing reaction product of P 8 and a polybutene of about1000 molecular weight, containing 5.3% Ba, 2.04% P, and 1.17% S SampleB-Sample A+0.75% quinolinol Sample B'-Sample A+1.00% quinolinol SampleCSample A+0.75% product of Example I Sample CSample A+0.20% product ofExample I Sample D-Sample A-|-0.75% product of Example II SampleD-Sample A+0.40% product of Example II Sample E-Sample A+l.0% product ofExample III Sample E-Sample A+0.75% product of Example III SampleE"Sample A+0.40% product of Example III Sample F-Sample A+0.75% productof Example IV Sample F-Sample A+O.40% product of Example IV SampleGSample A+0.75% product of Example V Sample G'Sample A+0.40% product ofExample V Sample H-Sample A+0.50% product of Example VI Sample ISampleA+0.75% product of Example VII Sample J--Sample A+0.75% product ofExample VIII Table I S. S. (1T.

Sample Acidity 1 Mg. Wt. Loss 24 hrs. 48 hrs. 72 hrs. 48 hrs. 72 hrs.

6. 16 12. 04 i6. 80 698 I, 360 4. 48 8. 40 12. 60 261 727 1. 68 5. 04 9.8 249 498 0.84 1.4 1.68 84 117 1. 14 2. 24 3. 04 25 34 2. 24 2. 8 3. 0839 60 1. 4 2. 52 2. 8 54 77 0. 84 1. 4 1. 68 57 68 0. 70 1. 4 1. 4 43 660. 98 7. ll. 0 180 468 2. 24 3. 64 3. 92 20 35 3.08 4. 2 5. 6 28 35 0.12 2. 24 7. 8 54 351 1. 4 4. 48 10.08 201 505 0. 84 1. 4 1. 8 71 1.121.68 1.86 51 95 1.12 4. 76 8. 4 165 392 Allowable weight losses in theabove test are 200 mg. at 48 hours and 500 mg. at; 72 hours.

1 Mg. KOH per gram of oil.

The higher molecular weight reaction products of this invention alsoexhibit detergency properties as demonstrated by the data in Table IIwhich were obtained by the following test, referred to as the IndianaStirring Oxidation Test (ISOT). In this test, 250 cc. of the oil to betested are heated at 330-332 F. in a 500 cc. glass beaker in thepresence of 5 square millimeters of copper and square millimeters ofiron. Four glass rods of 6 millimeter diameter are suspended in the oilwhich is stirred at about 1300 r.p.m. by means of a glass stirrer havinga 40 blade pitch. At intervals of 24, 48 and 72 hours, oil samples aretaken and acidity and sludge (naphtha insolubles) values determined. Theglass rods are inspected for evidence of varnish formation thereon.Varnish values are based on a visual rating in which glass rods free ofvarnish are rated '10 while badly varnishcoated rods are rated 1. Rodshaving appearances between these extremes are given intermediatenumerical values.

The following samples were subjected to the above test:

Sample 1-A solvent extracted SAE-3O base oil (control) Sample 2Sample1+1.0% product of Example III Sample 3Sample l+l.0% product of Example VTable 11 Sample Acidity 1 Varnish Naphtha Insolubles 24 48 72 hrs. 24 4872 24 48 72 hrs. hrs. hrs. hrs. hrs. hrs. hrs. hrs.

' 1 Mg. KOH per gram of oil.

The herein described 8-quinolinol-azomethine reaction products can beemployed in the form of a concentrate in a suitable oil base, theconcentrate containing from about 10% to about 50% or more of theadditives. Such concentrates are used for blending with a hydrocarbonoil or other oils in the proportions desired for the particularconditions of use so that upon further dilution with the oil, such as ahydrocarbon lubricating oil, a homogeneous mixture containing from about0.001% to about 10% of said additive is obtained.

Compositions containing the herein described reaction products ofS-quinolinol and azomethines can contain other additives such as pourpoint depressors, antioxidants, extreme pressure agents, V.I. improvers,antiwear agents, rust inhibitors, etc. of the type Well known in theart.

While this invention has been described in connection with the use ofthe herein described additives in lubricant compositions, their use isnot limited thereto; but the same can be used in products other thanlubricating oils, such as for example, insulating oils, greases,nondrying animal and vegetable oils, waxes, asphalts, etc.

Percentages given herein and in the appended claims are weightpercentages unless otherwise stated.

Although the present invention has been described with reference tospecific preferred embodiments thereof, the invention is not to beconsidered as limited thereto but includes within its scope suchmodifications and variations as come within the spirit of the appendedclaims.

Iclaim:

1. A lubricant composition comprising a major proportion of anoleaginous compound and from about 0.01% to about 10% of an oil-solublecompound selected from the class consisting of a compound having thegeneral structural formula in which R and R" are selected from the classconsisting of hydrogen, a hydrocarbon radical containing from 1 to about40 carbon atoms, and a heterocyclic radical containing from 1 to about40 carbon atoms, R is a hydrocarbon radical containing from 1 to about40 carbon atoms, and X is the remainder of the nucleus of an N- iieteroring selected from the class consisting of a 5- membered N-hetero ringand a 6-membered N-hetero ring.

2. A lubricant composition as described in claim 1 in which R and R arehydrogen and R is a butyl radical.

,3. A lubricant composition as described in claim 1 in 9 which R and R"are hydrogen and R is an alkyl radical having from about 18 to about 24atoms.

4. A lubricant composition as described in claim 1 in which R ishydrogen, and R" and R are ethyl radicals.

5. A lubricant composition as described in claim 1 in which R is aphenyl radical, R" is hydrogen, and R is a phenethyl radical.

6. A lubricant composition as described in claim 1 in which R is C H andX is the remainder of the nucleus of the piperidyl radical.

7. A lubricant composition as described in claim 1 in with theoleaginous compound is a lubricating oil.

8. A lubricant composition comprising a major proportion of alubricating oil, from about 0.002% to about 10% of a phosphorusandsulfur-containing neutralized phosphorus sulfide-hydrocarbon reactionproduct detergent lubricant additive, and from about 0.01% to about 10%of an oil-soluble compound selected from the class consisting of acompound having the general structural formula H and a compound havingthe general structural formula 9. A lubricant composition as describedin claim 8 in which the detergent additive is a barium-containingneutralized reaction product of P S and a polybutene.

10. An addition agent for lubricant compositionsconsisting essentiallyof a concentrated solution of hydrocarbon oil containing more than 10%of an oil-soluble compound selected from the class consisting of acompound having the general structural formula H and a compound havingthe general structural formula in which R and R are selected from theclass consisting of hydrogen, a hydrocarbon radical containing from 1 toabout 40 carbon atoms, and a heterocyclic radical containing from 1 toabout 40 carbon atoms, R is a hydrocarbon radical containing from 1 toabout 40 carbon atoms and X is the remainder of the nucleus of an N-hetero ring selected from the class consisting of a 5- membered N-heteroring and a G-membered N-hetero ring.

References Cited in the file of this patent UNITED STATES PATENTS2,198,961 Dietrich Apr. 30, 1940 2,223,411 Fuller et a1 Dec. 3, 19402,298,640 Prutton Oct. 13, 1942 2,316,082 Loane et. a1. Apr. 6, 19432,458,526 Oberright Ian. 11, 1949 FOREIGN PATENTS 738,093 Great BritainOct. 5, 1955 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No. 2,948,}680 August 9 1960 Ellis Ke Fields It is herebycertified that error appears in the printed specification 'e' ab of thove numbered patent requiring correction and that the said LettersPatent should read as corrected below.

Column 2, line l for "attaced" read attached column 6 line 4,, for"subseqauntly" read subsequently line 5, for "slovent" read solventcolumn 7, Table I under the heading "24 hrst" thirteenth item for "Oml2"read 1,12

Signed and sealed this llth day of April 1961,

(SEAL) Attest:

ERNEST w- ,SWI ARTHUR W. CROQ Attesting Officer A g Commissioner ofPatents Attest ing UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No. 2,948,680 I August 9 1960 Ellis K.a Fields It is herebycertified that error appears in the printed specification of the abovenumbered patent requiring correction and that the said Letters .Patentshould read as corrected below.

Column 2 line 1 for "attaced" read attached -g column 6, line 4 for"subseqeuntly" read subsequently line 5, for "slovent" read solventcolumn 7 Table I under the heading "'24 hrso" thirteenth item for "0.12"read 1012 'o Signed and sealed this 11th day of April 1961a (SEAL)Attest:

ERNEST w. s /woER ARTHUR W. CR C Acting Commissioner of Patents

1. A LUBRICANT COMPOSITION COMPRISING A MAJOR PROPORTION OF ANOLEAGINOUS COMPOUND AND FROM ABOUT 0.01% TO ABOUT 10% OF AN OIL-SOLUBLECOMPOUND SELECTED FROM THE CLASS CONSISTING OF A COMPOUND HAVING THEGENERAL STRUCTURAL FORMULA